CN103979646A - Continuous electric flocculation water treatment method for dosing along process - Google Patents
Continuous electric flocculation water treatment method for dosing along process Download PDFInfo
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Abstract
The invention discloses a continuous electric flocculation water treatment method for dosing along a process, which treats wastewater through continuous electric flocculation, wherein an aluminum or iron electrode serves as an anode; retention time is 10-60min; electrode voltage is 3-15V; electrode current density is 0.5-5mA/cm<2>; cell voltage is 3-20V; meanwhile, from an inlet to an outlet, a continuous electric flocculation electrolysis cell is divided into a front section, a middle section and a rear section along a flowing direction of wastewater; at least one of an acid-alkali chemical, a flocculating agent and a salt ion chemical is added from the inlet of each section. By improvement of an electric flocculation process, the water treatment method disclosed by the invention can relieve a problem of anodic passivation, improve hydroxide floc yield and increase floc absorption efficiency.
Description
Technical field
The present invention relates to a kind of electricity flocculation water treatment method, relate in particular to a kind of continuous electricity flocculation water treatment method along flow process dosing, belong to water treatment field.
Background technology
Electricity flocculation claims again electric flocculating.In electric flocculation process, sacrificial anode (Fe or Al) electrolytic production of metals positively charged ion, negative electrode water electrolysis produces H
2and OH
-, metallic cation and OH under electric field action
-electromigration occurs, and in solution, interosculating and being hydrolyzed generates monokaryon or multinuclear oxyhydroxide flco, is finally formed with high-specific surface area and contains the oxyhydroxide flco that enriches surface hydroxyl.By cooperation adsorb, net catches that volume is swept, toxic substance in the effect such as adsorption bridging planar water.A large amount of O that electrochemical reaction process produces
2and H
2microbubble can be adsorbed on pollutent flco surface, produces air supporting effect, and the collaborative Pollutants in Wastewater of removing, realizes good solid-liquid separation effect.Whole electric flocculation process has comprised electrolytic flocculation, electrofloatation and electrolytic oxidation reduction, as the synergistic effect of the treating processess such as anodic oxidation, cathodic reduction (impurity and heavy metal ion) and colloidal particle electric discharge and flocculation, ion-conductance migration.In Treatment of Industrial Water mainly there is the problem that electrode passivation and flco output and adsorption efficiency are not high in electric flocculation process at present at present, and these several problems have finally caused the not high result of electric flocculation process clearance.
For electrode passivation problem, investigator is applied in EC above by high-frequency impulse and periodic reverse power technology both at home and abroad, has improved preferably electrode passivation problem, has reduced energy consumption simultaneously.But it is higher that the defect of this type of power technology is economic input, high frequency pulse power supply fancy price makes this power technology cost of investment in electricity flocculation sewage disposal higher.Yield poorly and the not high problem of adsorption efficiency for flco, existing scholar is studied this, but not yet draws remarkable effect.
Summary of the invention
Goal of the invention: the object of this invention is to provide one electric flocculation process is improved, can slow down anode passivation problem, improve oxyhydroxide flco output, improve the continuous electricity flocculation water treatment method along flow process dosing of flco adsorption efficiency.
Summary of the invention: of the present invention along the continuous electricity flocculation of flow process dosing water treatment method, flocculate waste water is processed with continuous electricity, wherein, anode adopts aluminium or the ferroelectric utmost point, the residence time is 10～60min, and electrode voltage is 3～15V, and electrode current density is 0.5～5mA/cm
2, bath voltage is 3～20V; Meanwhile, along waste water flow direction continuously electricity flocculation electrolyzer from import to outlet, be divided into before, during and after three sections, every section of ingress adds at least one in soda acid medicament, flocculation agent or salt ion medicament.
Wherein, described before, during and after in three sections, every section is made up of at least 1 group, its summation is 3～5 groups.Described waste water is effluent containing heavy metal ions or brine waste, and wherein, heavy metal ion or salt ion total concn are 50～500ppm.
The mode that adds of described soda acid medicament is: it is 4～6 that leading portion ingress adds acid medicine to regulate waste water ph; It is 6～7 that ingress, stage casing adds acid medicine to regulate waste water ph; For effluent containing heavy metal ions, it is 7～8 that back segment ingress adds acidity or basic agent to regulate waste water ph, and for brine waste, it is 6～7 that back segment ingress adds acidity or basic agent to regulate waste water ph.
The mode that adds of described flocculation agent is: leading portion and ingress, stage casing all do not add flocculation agent, only add flocculation agent at back segment entrance.Described flocculation agent is polymerization aluminum chloride, polyferric chloride or PAM, and the dosage adding is 1～10ppm.
The mode that adds of described salt ion medicament is, only adds salt ion medicament in leading portion ingress, and stage casing and back segment all do not add.Described salt ion medicament is aluminium salt or molysite, and wherein, aluminium salt is aluminum chloride or Tai-Ace S 150, and molysite is iron trichloride or ferric sulfate.
The electric flocculation system that is the ferroelectric utmost point for anode, adds aluminum chloride, and the dosage adding is 5～20ppm, adds iron trichloride, and the dosage adding is 10～50ppm; Be the electric flocculation system of aluminium electrode for anode, add aluminum chloride or Tai-Ace S 150, the dosage adding is 10～50ppm, adds ferric sulfate or iron trichloride, and the dosage adding is 5～20ppm.
Beneficial effect: the present invention compared with prior art, its remarkable advantage is: electric flocculation process comprises multistep chemical reaction and sepn process, the optimum process condition difference of these processes, the electricity electrolyzer passage that flocculates is divided into multistage by the present invention, Mei Duan ingress adds respectively the medicament of various dose, this adjusts the electrolytic flocculation and the adsorption process that are conducive to for electrolyzer passage different positions, to adapt to each section of reaction and separation processes process that accounts for Main Function, to reach the optimum process condition of each process; Process modification by aforesaid method to electric flocculation process, can slow down anode passivation problem, improves oxyhydroxide flco output, improves flco adsorption efficiency.
Brief description of the drawings
Fig. 1 is Al in the continuous electric flocculation process of two-dimensional steady-state of the present invention
3+the distribution plan of concentration;
Fig. 2 is OH in the continuous electric flocculation process of two-dimensional steady-state of the present invention
-the distribution plan of concentration;
Fig. 3 is Al (OH) in the continuous electric flocculation process of two-dimensional steady-state of the present invention
3the distribution plan of concentration.
Embodiment
Below technical scheme of the present invention is elaborated.
Yield poorly and the not high problem of adsorption efficiency for the flco of current existence, we attempt in the ingress of EC process early stage or electrolysis passage directly disposable aluminium salt or the molysite medicament of adding and, to improve flco output, add flocculation agent and soda acid medicament to improve the adsorption efficiency of flco.But in the electrolysis passage due to electricity flocculation continuously, comprise multiple processes, if the generation of the hydrolysis of soluble anode electrolytic production of metals positively charged ion, electrolysate iron ion (or aluminum ion), iron (or aluminium) oxyhydroxide absorption flco, absorption flco are to heavy metal ion or organic absorption.These processes occur in different positions and have different processing condition, are therefore unifiedly not suitable for the processing condition of each process in electricity flocculation in the disposable dosing in ingress.Therefore, we extend to the thinking of dealing with problems the division of continuous electricity flocculation electrolysis passage, consider to add medicament at passage different positions, specific as follows: for explaining and analyze thinking of the present invention, continuous electric flocculation technique to be carried out to two Dimension Numerical Value calculating simulation for hydromeehanics and the mass transfer model of the process of heavy-metal ion removal.Model selection aluminium electrode is anode and negative electrode, and the length of the electrolysis passage of electricity flocculation is 320mm, and interelectrode distance is 10mm, and electrode length is 300mm, and fluid flows from left to right, and the residence time of fluid is 10 minutes, and current density society is 1mA/cm
2, the ionogen in solution is elected sodium sulfate as, and heavy metal ion to be removed is cadmium ion, and concentration is 100ppm.The be hydrolyzed to level Four of the aluminum ion that setting anode electrolysis produces in the aqueous solution is hydrolyzed.The transmission control partial differential equation of model are: the Navier-Stokes equation that fluid mechanics equation is incompressible fluid, the mass transfer equation of each component ion is Nernst-Planck equation, comprises the convective-diffusive equation of electromigration picture.Adopt finite element analysis software to solve model.Fig. 1-3 are the result after model solution, and Fig. 1-3 are respectively Al
3+, OH
-and Al (OH)
3concentration distribution.
Soda acid medicament:
At the leading portion of the whole flow process of electrolysis passage, in electrolysis passage, aluminium ion concentration is higher, aluminum ions hydrolysis reaction is lower, its solubility hydrolysate aluminium hydroxide ionic concn is lower, and the amount of its soluble ferro-aluminum oxyhydroxide (i.e. rate oxyhydroxide flco) is also lower, therefore oxyhydroxide flco is less to the adsorptive capacity of material to be removed.Therefore this section produces aluminum ion as master is (from the model calculation (Fig. 1), at leading portion region Al taking electrolysis
3+concentration higher).Because acid system is conducive to the aluminium stripping electrode reaction of aluminium electrode, and the model calculation visible (Fig. 2), front-end position OH
-concentration is higher, so should reduce the pH value of solution in section, improves the acidity of solution, and EC import pH is adjusted to 4～6.
At the interlude of the whole flow process of electrolysis passage, in this section, the concentration of aluminum ion and hydrolysate thereof increases, pH value meta-alkalescence, aluminum ions hydrolysis rate is higher, oxyhydroxide flco generating rate is higher, flco generation is larger, so the process that section relates generally to is the generation of aluminum ions hydrolysis and aluminium hydroxide flco.The pH of interlude ingress value is between 6～7, and fluid is through the electrolytic reaction of second segment, and pH value will raise 2～3, and outlet will be in 8～9 intervals.In electrolyzer, the pH value size of each section can be from OH
-concentration distribution (Fig. 2) is found out.Because the optimal ph of aluminium electrode stripping reaction is slightly acidic, and aluminum ion hydrolysis and then the optimal ph that is converted into the reaction of aluminium hydroxide flco are 7～8, therefore need to improve interlude import acidity, the pH value of middle import are adjusted to 6～7.
At the back segment of the whole flow process of electrolysis passage, this fragment position aluminum ion hydrolysis rate is higher, and (this can find out from Fig. 3 of the model calculation, Al (OH)
3concentration start concentration from rear end and increase comparatively fast, its hydrolysis rate is higher).Because aluminum ion hydrolysis reaction develops to depth direction, in this section, aluminum ion transforms to oxyhydroxide flco gradually, the aluminium hydroxide ionic concn of solubility reduces gradually, the concentration of insolubility aluminium hydroxide flco reaches the highest, and aluminum ions concentration is extremely low simultaneously, far below the concentration of its hydrolysate.So section relates generally to generation and the absorption of flco to ion to be removed of aluminium hydroxide flco.Because aluminium hydroxide flco is the porous mass that has high reference area, its highdensity surface hydroxyl is by the pollutent in the mode Separation of Water by exclusive absorption and non-exclusive absorption.Realize and separating thereby the mode generation complex reaction that exclusive absorption is mainly carried out respectively coordination reaction and ligand exchange by hydroxyl part and heavy metal ion and negatively charged ion adsorbs these ions.And organic pollutant is mainly realized and being separated by the non-exclusive absorption of porous flco.For heavy metal ion, mainly separate with non-exclusive absorption by exclusive absorption, exclusive absorption carry out Coordination Adsorption and coordination reaction by surface hydroxyl part to heavy metal ion, separate thereby realize, porous flco will carry out electrostatic attraction to heavy metal ion simultaneously, and in the time that electrostatic attraction separates, flco is electronegative will more be conducive to flco absorption.And for negatively charged ion (as fluorion, nitrate ion and arsonium ion etc.), the flco of positively charged will be conducive to electrostatic attraction.Therefore at the back segment of electrolyzer passage, for different system waste water, need to adopt different soda acid dosing dosage.Be effluent containing heavy metal ions system for material to be removed, need to take into account the non-exclusive absorption of flco, need to make flco electronegative to realize higher non-exclusive adsorption.The waste water system that is negatively charged ion for material to be removed, need to make flco positively charged to realize higher non-exclusive adsorption.Therefore the waste water system that is heavy metal ion for material to be removed, according to epimere water outlet pH value, need to be adjusted into 7～8 by back segment import pH value; The waste water system that is negatively charged ion for material to be removed, need to add acid medicine, and rear end import water is adjusted into acidity, and pH is 6～7.
Can be summarized as, leading portion is mainly aluminum ion production process, and interlude is mainly the process that aluminum ion generation and hydrolysis reaction and flco thereof form, and rear end is mainly the process of aluminum ion generation, flco formation and flco adsorption zone separated portion.Due to the carrying out along with electrolytic process, along fluid flow direction in electrolysis passage, along with catholyte liberation of hydrogen and produce OH
-, pH value increases gradually, even if aluminum ions hydrolysis consumes a part of OH
-but, the speed that the speed that negative electrode produces will consume higher than aluminum ion hydrolysis, pH value still presents the trend of increase.Due under slant acidity condition, aluminium electrode is not easy to occur passivation layer, and anode has higher overpotential for oxygen evolution and lower aluminium stripping overpotential, the therefore anodic reaction in the relatively more applicable electric flocculation process of acidic conditions under acidic conditions.Thereby this reduces on the one hand anode passivation and reduces bath voltage, improve current efficiency thereby reduce on the other hand oxygen evolution reaction.If (but add whole acid at first paragraph entrance, instead of segmentation adds.Too high acidity will make the rate reduction of aluminum ion hydrolysis, and this will reduce the output of absorption flco, and a large amount of aluminum ions will remain in solution.)
Salt ion medicament:
Meanwhile, because producing aluminum ions while negative electrode generation water electrolysis, anode produces OH
-, produce three OH of an aluminum ions generation simultaneously
-, the flux that therefore aluminum ion produces is OH
-1/3.Because aluminum ion hydrolysis reaction is polystep reaction, therefore at the early stage of total residence time, OH
-excessive, aluminum ion is a small amount of.Therefore need to be at the leading portion of the residence time, the fore portion of total electrolyzer passage additionally adds aluminium salt, to improve aluminium ion concentration, thereby realizes higher oxyhydroxide flco output.
The electric flocculation process that is the ferroelectric utmost point for anode, the reaction that anode mainly occurs is that iron is separated out and changed ferrous ion into from anode.After ferrous ion enters solution, form iron hydroxyl flco thereby a part self is hydrolyzed into ferrous hydroxide, ferrous ion also can react with water oxygen gas under alkaline condition on the other hand, is oxidized by oxygen as ferric ion.From the adsorptive power angle analysis of divalence and ferric hydroxide flco, the latter can provide the more highdensity surface hydroxyl with Coordination Adsorption ability.Therefore on electric flocculation process, need to change ferrous ion as much as possible into ferric ion.Traditional method is aeration, but aeration is unfavorable for the formation of flco and stable, even if under alkaline condition aeration, its degree of oxidation is also lower.To adopt iron trichloride as molysite, at the disposable iron trichloride that adds in electrolyzer passage leading portion ingress, chlorion enters after solution on the one hand, and part chlorion will be analysed chlorine reaction at anode, produce chlorine, thereby chlorine dissolves and makes oxidation of divalent iron ion in solution; Adding raising iron concentration to improve flco output of ferric ion on the other hand.
Flocculation agent:
To adsorb the adsorption efficiency of flco to material to be removed in order improving in electric flocculation process, the flco coacervation disperseing need to be formed to larger flco, therefore need to add flocculation agent.In electric flocculation process intermittently, be generally in follow-up flocculation basin, to add flocculation agent and coagulant aids.In continuous electric flocculation process, be generally to add flocculation agent in electrolyzer ingress or follow-up flocculation basin.If add flocculation agent in ingress, this can make the flco that electrolyzer passage leading portion produces form larger flco cluster, and the existence of flco cluster will hinder OH in solution
-enter contacting of the inner aluminium hydroxide flco of cluster and cluster, this reduces the density of the surface hydroxyl of flco.If add flocculation agent in subsequent technique flocculation basin, although this can make flco realize the reunion of higher degree, the appearance of flocculation basin increases total treatment cycle.Therefore need the to flocculate back segment ingress of electrolyzer passage adds flocculation agent.The waste water of handling directly enters settling tank from electricity flocculation electrolysis passage, and does not need flocculation basin.
Embodiment 1:
With continuous electric flocculation process, the heavy metal wastewater thereby containing cadmium is processed, the total concn of heavy metal ion is 50ppm, and anode and cathode adopts aluminium electrode, and the residence time is 10min, and electrode voltage is 3V, and electrode current density is 0.5mA/cm
2.Be specially along waste water flow direction, from import to outlet, can be divided into 3 sections, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose, is specially along flow direction,
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 5 that the 1st section of import adds acid medicine to adjust pH value.The 2nd section adds acid medicine to adjust pH value is 6.The 3rd section adds acidity or basic agent to make back segment water inlet pH be adjusted into 7.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
The 1st section and the 2nd section of import do not add flocculation agent, only add flocculant poly iron trichloride the 3rd section of import, and the dosage adding is 1ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
The 2nd section and the 3rd section of import do not add salt ion medicament, only add saliferous ion medicament to enter Tai-Ace S 150 the 1st section of import, and the dosage adding is 10ppm, adds ferric sulfate, and the dosage adding is 5ppm.
The content that detects this heavy metal in waste water cadmium in exit is 3.7ppm, and clearance is 92.6%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, the content that detects heavy metal in waste water cadmium in exit is 7.1, and clearance is 85.5%.
Embodiment 2:
With continuous electric flocculation process, the waste water containing nickel ion is processed, the total concn of nickel ion is 500ppm, and anode and cathode adopts the ferroelectric utmost point, and the residence time is 60min, and electrode voltage is 15V, and electrode current density is 5mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into front in rear 3 sections 5 groups, wherein, leading portion is the 1st group, and stage casing is the 2nd, 3 liang of groups, back segment is the 4th, 5 liang of groups, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose.Be specially along flow direction,
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 4 that the 1st group of import adds acid medicine to adjust pH value.The 2nd group adds acid medicine to adjust pH value is 6.The 3rd group adds acidity or basic agent to make this section of water inlet pH be adjusted into 6, the 4 groups to add acidity or basic agent to make this section of water inlet pH be adjusted into 7, the 5 groups to add acidity or basic agent to make this section of water inlet pH be adjusted into 8.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
1st～3 groups of imports do not add flocculation agent, add flocculant poly aluminum chloride the 4th group and the 5th group of import, and the dosage adding is 10ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
2nd～5 groups of imports do not add salt ion medicament, only add saliferous ion medicament the 1st group of import, add aluminum chloride, and the dosage adding is 20ppm, adds iron trichloride, and the dosage adding is 50ppm.
The content that detects this heavy metal in waste water nickel in exit is 55.9ppm, and clearance is 88.8%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, the content that detects heavy metal in waste water nickel in exit is 122.4ppm, and clearance is 75.5%.
Embodiment 3:
With continuous electric flocculation process, the waste water of fluoride ion is processed, the total concn of fluorion is 100ppm, and anode and cathode adopts the ferroelectric utmost point, and the residence time is 30min, and electrode voltage is 7.5V, and electrode current density is 2.5mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into front in rear 3 sections 4 groups, wherein, leading portion is the 1st group, stage casing is 2,3 liang of groups, back segment is at least one in the 4th group every section flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose.Be specially along flow direction,
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 5 that the 1st group of import adds acid medicine to adjust pH value.The 2nd group adds acid medicine to adjust pH value is 6.The 3rd group adds acidity or basic agent to make this section of water inlet pH be adjusted into 7, the 4 groups to add acidity or basic agent to make this section of water inlet pH be adjusted into 8.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
I.e. 1st～3 groups of imports in leading portion and stage casing do not add flocculation agent, add flocculant poly aluminum chloride in i.e. the 4th group of import of back segment, and the dosage adding is 5ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
I.e. 2nd～4 groups of imports of stage casing and back segment do not add salt ion medicament, only add saliferous ion medicament in i.e. the 1st group of import of leading portion, add aluminum chloride, and the dosage adding is 10ppm, adds iron trichloride, and the dosage adding is 30ppm.
The content that detects this heavy metal in waste water cadmium in exit is 4.5ppm, and clearance is 95.5%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, the content that detects fluorine in wastewater in exit is 12.4ppm, and clearance is 87.6%.
Embodiment 4:
With continuous electric flocculation process, the waste water containing chromium ion is processed, the total concn of chromium ion is 350ppm, and anode and cathode adopts the ferroelectric utmost point, and the residence time is 50min, and electrode voltage is 15V, and electrode current density is 4.2mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into front in rear 3 sections 5 groups, wherein, leading portion is the 1st group, and stage casing is the 2nd, 3 liang of groups, back segment is the 4th, 5 liang of groups, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose.Be specially along flow direction,
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 5 that the 1st group of import adds acid medicine to adjust pH value.The 2nd group adds acid medicine to adjust pH value is 6.5.The 3rd group adds acidity or basic agent to make this section of water inlet pH be adjusted into 6, the 4 groups to add acidity or basic agent to make this section of water inlet pH be adjusted into 8, the 5 groups to add acidity or basic agent to make this section of water inlet pH be adjusted into 8
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
1st～3 groups of imports do not add flocculation agent, add flocculant poly iron trichloride the 4th group and the 5th group of import, and the dosage adding is 8ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
2nd～5 groups of imports do not add salt ion medicament, only add saliferous ion medicament the 1st group of import, add aluminum chloride, and the dosage adding is 40ppm, adds ferric sulfate, and the dosage adding is 15ppm.
The content that detects this heavy metal in waste water chromium in exit is 25.2ppm, and clearance is 92.8%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, the content that detects heavy metal in waste water chromium in exit is 48.6ppm, and clearance is 86.1%.
Embodiment 5:
With continuous electric flocculation process, the waste water containing arsonium ion is processed, the total concn of arsonium ion is 150ppm, and anode and cathode adopts the ferroelectric utmost point, and the residence time is 25min, and electrode voltage is 10V, and electrode current density is 2.5mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into 3 sections, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose.Be specially along flow direction,
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 6 that the 1st section of import adds acid medicine to adjust pH value.The 2nd section adds acid medicine to adjust pH value is 6.5.The 3rd section adds acidity or basic agent to make this section of water inlet pH be adjusted into 8.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
1st～2 sections of imports do not add flocculation agent, add flocculant poly aluminum chloride the 3rd section of import, and the dosage adding is 7ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
2nd～3 sections of imports do not add salt ion medicament, only add saliferous ion medicament the 1st section of import, add aluminum chloride, and the dosage adding is 12ppm, adds iron trichloride, and the dosage adding is 25ppm.
The content that detects this heavy metal in waste water arsenic in exit is 9.75ppm, and clearance is 93.5%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, the content that detects heavy metal in waste water arsenic in exit is 18.4ppm, and clearance is 87.7%.
Embodiment 6:
With continuous electric flocculation process, the mixture-metal waste water containing chromium, nickel and copper is processed, the concentration of chromium, nickel and copper is 150ppm, and anode and cathode adopts the ferroelectric utmost point, and the residence time is 50min, and electrode voltage is 15V, and electrode current density is 4.6mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into front in rear 3 sections 5 groups, wherein, leading portion is the 1st group, and stage casing is the 2nd, 3 liang of groups, and back segment is the 4th, 5 liang of groups, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose, is specially along flow direction
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 5 that the 1st group of import adds acid medicine to adjust pH value.The 2nd group adds acid medicine to adjust pH value is 6.The 3rd group adds acidity or basic agent to make back segment water inlet pH be adjusted into 6.5.The 4th group adds acidity or basic agent to make back segment water inlet pH be adjusted into 7.The 5th group adds acidity or basic agent to make back segment water inlet pH be adjusted into 7.5.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
1st～3 groups of imports do not add flocculation agent, add flocculant poly iron trichloride the 4th group and the 5th group of import, and the dosage adding is 10ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
2nd～5 groups of imports do not add salt ion medicament, only add saliferous ion medicament to enter aluminum chloride the 1st group of import, and the dosage adding is 15ppm, adds into iron trichloride, and the dosage adding is 40ppm.
The content that detects each heavy metal species in this waste water in exit, the concentration of chromium, nickel and copper is respectively 9.6ppm, 3.75ppm and 4.65ppm, and clearance is respectively 93.6%, 97.5% and 96.9%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, detect the content of each heavy metal species in waste water in exit, the concentration of chromium, nickel and copper is respectively 24.9ppm, 14.9ppm and 20.4ppm, and clearance is respectively 85.4%, 90.1%, 86.4%.
Embodiment 7:
With continuous electric flocculation process, to processing containing the mixture-metal waste water of cadmium and zinc, chromium and zinc concentration are 200ppm, and anode and cathode adopts aluminium electrode, and the residence time is 55min, and electrode voltage is 15V, and electrode current density is 4.7mA/cm
2.Along waste water flow direction, from import to outlet, can be divided into front in rear 3 sections 4 groups, wherein, leading portion is the 1st group, and stage casing is the 2nd, 3 liang of groups, and back segment is the 4th group, at least one in every section of flocculation agent, coagulant aids or soda acid medicament that adds respectively various dose, is specially along flow direction
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of soda acid medicament is:
It is 5.5 that the 1st group of import adds acid medicine to adjust pH value.The 2nd group adds acid medicine to adjust pH value is 6.The 3rd group adds acidity or basic agent to make back segment water inlet pH be adjusted into 7.The 4th group adds acidity or basic agent to make back segment water inlet pH be adjusted into 8.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of flocculation agent is:
1st～3 groups of imports do not add flocculation agent, add flocculant poly iron trichloride the 4th group of import, and the dosage adding is 8ppm.
From the import of continuous electricity flocculation electrolyzer to outlet, the method that adds of aluminium salt or molysite is:
2nd～4 groups of imports do not add salt ion medicament, only add saliferous ion medicament to enter Tai-Ace S 150 the 1st group of import, and the dosage adding is 45ppm, adds into ferric sulfate, and the dosage adding is 17ppm.
The content that detects each heavy metal species in this waste water in exit, cadmium and zinc concentration are respectively 11.2ppm, and 7.8ppm, and clearance is respectively 94.4% and 96.1%.
For contrasting, adopt same continuous electric flocculation process to process same waste water, add soda acid medicament, flocculation agent and the salt ion medicament that same gradation add-on is identical the ingress of whole electrolyzer passage is disposable, detect the content of each heavy metal species in waste water in exit, cadmium and zinc concentration are respectively 23.2ppm and 30ppm, clearance is respectively 88.4%, 85.0%.
Claims (9)
1. along the continuous electricity flocculation of a flow process dosing water treatment method, it is characterized in that: flocculate waste water is processed with continuous electricity, wherein, anode adopts aluminium or the ferroelectric utmost point, the residence time is 10～60min, and electrode voltage is 3～15V, and electrode current density is 0.5～5mA/cm
2, bath voltage is 3～20V; Meanwhile, along waste water flow direction continuously electricity flocculation electrolyzer from import to outlet, be divided into before, during and after three sections, every section of ingress adds at least one in soda acid medicament, flocculation agent or salt ion medicament.
2. according to claim 1 along flow process dosing electricity flocculation water treatment method continuously, it is characterized in that: before, during and after described, in three sections, every section is made up of at least 1 group, and its summation is 3～5 groups.
According to described in claim 1 or 2 along continuously electricity flocculation water treatment method of flow process dosing, it is characterized in that: described waste water is effluent containing heavy metal ions or brine waste, wherein, heavy metal ion or salt ion total concn are 50～500ppm.
4. according to claim 3 along flow process dosing electricity flocculation water treatment method continuously, it is characterized in that the mode that adds of described soda acid medicament is: it is 4～6 that leading portion ingress adds acid medicine to regulate waste water ph; It is 6～7 that ingress, stage casing adds acid medicine to regulate waste water ph; For effluent containing heavy metal ions, it is 7～8 that back segment ingress adds acidity or basic agent to regulate waste water ph, and for brine waste, it is 6～7 that back segment ingress adds acidity or basic agent to regulate waste water ph.
According to described in claim 1 or 2 along continuously electricity flocculation water treatment method of flow process dosing, it is characterized in that the mode that adds of described flocculation agent is: leading portion and ingress, stage casing all do not add flocculation agent, only add flocculation agent at back segment entrance.
6. according to claim 5 along flow process dosing electricity flocculation water treatment method continuously, it is characterized in that: described flocculation agent is polymerization aluminum chloride, polyferric chloride or PAM, the dosage adding is 1～10ppm.
According to described in claim 1 or 2 along continuously electricity flocculation water treatment method of flow process dosing, it is characterized in that the mode that adds of described salt ion medicament is, only add salt ion medicament in leading portion ingress, stage casing and back segment all do not add.
8. according to claim 7 along flow process dosing electricity flocculation water treatment method continuously, it is characterized in that: described salt ion medicament is aluminium salt or molysite, wherein, aluminium salt is aluminum chloride or Tai-Ace S 150, and molysite is iron trichloride or ferric sulfate.
9. according to claim 8 along flow process dosing electricity flocculation water treatment method continuously, it is characterized in that: the electric flocculation system that is the ferroelectric utmost point for anode, add aluminum chloride, the dosage adding is 5～20ppm, add iron trichloride, the dosage adding is 10～50ppm; Be the electric flocculation system of aluminium electrode for anode, add aluminum chloride or Tai-Ace S 150, the dosage adding is 10～50ppm, adds ferric sulfate or iron trichloride, and the dosage adding is 5～20ppm.
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